The first catalytic enantioselective γ-boryl substitution of CF -substituted alkenes is reported. A series of CF -substituted alkenes was treated with a diboron reagent in the presence of a copper(I)/Josiphos catalyst to afford the corresponding optically active γ,γ-gem-difluoroallylboronates in high enantioselectivity. The thus obtained products could be readily converted into the corresponding difluoromethylene-containing homoallylic alcohols using highly stereospecific allylation reactions.
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http://dx.doi.org/10.1002/anie.201803663 | DOI Listing |
J Agric Food Chem
December 2024
College of Plant Protection, Southwest University, Chongqing 400715, China.
Etoxazole, a widely used mite growth inhibitor, contains a chiral center in its chemical structure, resulting in two mirror-image enantiomers. These enantiomers of etoxazole display significant differences in biological activity and environmental behavior. In bioassays conducted against , it was observed that S-etoxazole demonstrated approximately 279.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Compared with chiral β-amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining chiral β-amino phosphorus derivatives remains a challenge. These derivatives, which cannot be derived from chiral natural amino acids, possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of chiral β-amino phosphorus derivatives from -β-enamido phosphorus compounds is reported by using a green and low-cost earth-abundant metal nickel catalyst (13 examples of 99% ee).
View Article and Find Full Text PDFAppl Microbiol Biotechnol
December 2024
Department of Life Science and Technology: Tokyo Kogyo Daigaku Seimei Rikogakuin Seimei Rikogakukei, Institute of Science Tokyo, 4259 Nagatsuta-Cho Midzeori-Ku, Yokohama, 226-8501, Japan.
Chiral diaryl alcohols, such as (4-chlorophenyl)(pyridin-2-yl)methanol, are important intermediates for pharmaceutical synthesis. However, using alcohol dehydrogenases (ADHs) in the asymmetric reduction of diaryl ketones to produce the corresponding alcohols is challenging due to steric hindrance in the substrate binding pockets of the enzymes. In this study, the steric hindrance of the ADH from Geotrichum candidum NBRC 4597 (G.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Here, we report the enantioselective total syntheses of four diepoxy--kaurane diterpenoids including (-)-Macrocalin B, (-)-Acetyl-macrocalin B, and (-)-Isoadenolin A and the revised structure of (-)-Phyllostacin I, which hinges on the strategic design of a regioselective and stereospecific trapping of a highly reactive [3.2.1]-bridgehead enone intermediate via a tethered intramolecular Diels-Alder reaction.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR 999077, China.
Catalytic enantioselective substitution of the readily available racemic α-halo carbonyl compounds by nitrogen nucleophiles represents one of the most convenient and direct approaches to access enantioenriched α-amino carbonyl compounds. Distinct from the two available strategies involving radicals and enolate ions, herein we have developed a new protocol featuring an electronically opposite way to weaken/cleave the carbon-halogen bond. A suitable chiral anion-based catalyst enables effective asymmetric control over the key positively charged intermediates.
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